Novel Whitening Agents for Cellulosic Substrates

ABSTRACT

The present application relates to novel whitening agents for cellulosic substrates. The whitening agents are comprised of at least two constituents: at least one chromophore constituent and at least one polymeric constituent. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to light, or they may absorb light to reflect these same shades. The whitening agents are further characterized by the polymeric component comprising at least two repeating glycerol units. This disclosure also relates to laundry care compositions including but not limited to liquid and/or powder laundry detergent formulations and rinse added fabric softening (RAFS) compositions that comprise such whitening agents.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority to U.S. patent application Ser. No.16/180,169 filed Nov. 5, 2018, which claims priority to U.S. patentapplication Ser. No. 15/283,460 filed Oct. 3, 2016, which claimspriority under 35 U.S.C. § 119(e) to U.S. Provisional Application Ser.No. 62/240,587 filed Oct. 13, 2015, all of which are hereby entirelyincorporated by reference.

TECHNICAL FIELD

The present application relates to novel whitening agents for cellulosicsubstrates. The whitening agents are comprised of at least twoconstituents: at least one chromophore constituent and at least onepolymeric constituent. Suitable chromophore components generallyfluoresce blue, red, violet, or purple color when exposed to light, orthey may absorb light to reflect these same shades. The whitening agentsare further characterized by the polymeric component comprising at leasttwo repeating glycerol units. These whitening agents may be ideal foruse in laundry care compositions including but not limited to liquidand/or powder laundry detergent formulations and rinse added fabricsoftening (RAFS) compositions.

BACKGROUND

The use of whitening agents, either optical brighteners or blueingagents, in textile applications is well known in the prior art. Astextile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. Thus, the purpose of whitening agents isgenerally to visually brighten these textile substrates and counteractthe fading and yellowing of the substrates. Typically, whitening agentsmay be found in laundry detergents, fabric softeners, or rinse aids andare therefore applied to textile substrates during the launderingprocess. However, it is important that whitening agents function tobrighten treated textile substrates without causing undesirable stainingof the textile substrates.

Cellulosic substrates, in particular, tend to exhibit a yellow hue afterexposure to light, air, and/or soiling. This yellowness is oftendifficult to reverse by normal laundering procedures. As a result, thereexists a need for improved whitening agents which are capable ofeliminating the yellowness exhibited by ageing cellulosic substrates. Byutilizing such improved whitening agents, the life of the textilesubstrates, such as clothing articles, bed and table linens, towels,etc., may be extended. The present whitening agent offers advantagesover U.S. Pat. Nos. 4,137,243, 5,039,782 and US Patent ApplicationPublication No. 2005/0288206 as the present whitening agent takesadvantage of compounds having at least two repeating glycerol units andwhich emit light with wavelengths in the range of blue, red, violet,purple, or combinations thereof upon exposure to ultraviolet light (or,they absorb light to produce the same shades) in order to neutralize theyellowness of cellulosic substrates. The present compounds functionideally as whitening agents for substrates comprised of cellulose,polyester, nylon and mixtures thereof and may be incorporated intolaundry detergent formulations for use by consumers during thelaundering process.

SUMMARY OF INVENTION

The present disclosure relates to laundry care compositions comprising alaundry care ingredient and a whitening agent. The whitening agent is anonionic amphiphilic nitrogen-linked polyglycerol dye having achromophore constituent selected from the group consisting of acridines,anthraquinones, azines, azos, benzodifuranes, benzodifuranones,carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethanes,formazans, hemicyanines, indigoids, methanes, naphthalimides,naphthoquinones, nitros, nitrosos, oxazines, phthalocyanines, pyrazoles,stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes andmixtures thereof.

The present disclosure also relates to laundry care compositioncomprising a laundry care ingredient and a whitening agent, thewhitening agent comprising at least one chromophore component thatcomprises a thiophene colorant and at least one polymeric component. Theat least one polymeric component comprise a[(CH₂CH₂O)_(x)(CH₂C(OR)HCH₂O)_(y)(CH₂CH₂O)_(z′)H] group. Each R isindependently selected from the group consisting of H, (CH₂CH₂O)_(z′)H,and mixtures thereof. The groups indicated by indices x, y and z may bearranged in any order and x=0 to 10, 1≤y≤5 and at least one y≥2.Independently each z=0 to 5 and each z′=0 to 5.

The present disclosure also relates to laundry care compositionsincluding but not limited to liquid and/or powder laundry detergentformulations and rinse added fabric softening (RAFS) compositions thatcomprise such whitening agents.

DETAILED DESCRIPTION

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, bar formand/or flake type washing agents and/or fabric treatment compositions.

As used herein, the term “fabric treatment composition” includes, unlessotherwise indicated, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions and combinations there of.Such compositions may be, but need not be rinse added compositions.

As used herein, the articles including “the”, “a” and “an” when used ina claim, are understood to mean one or more of what is claimed ordescribed.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the term “non-ionic” refers to any of many organiccompounds devoid of cationic or anionic substituents and thus lackingany ionic charge at a neutral pH.

As used herein, the term “amphiphilic” refers to any of many organiccompounds composed of hydrophilic and hydrophobic portions. A compoundis determined to be amphiphilic for the purposes of the presentinvention when the compound partitions between deionized water anddodecane at 25° C. such that the compound is predominantly in the waterlayer. Amphiphilic compounds are determined to be amphiphilic whiteningagents if the amphiphilic compound qualifies as a shading dye accordingto the test methods disclosed herein.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

The whitening agents of the present invention may be dyes, pigments, orpolymeric colorants comprising a chromophore constituent and a polymericconstituent covalently bound to one another. It will be understood bythose skilled in the art that the whitening agents are not two separatemolecules, one comprising a chromophore and the other comprising apolymer, but rather one molecule and that the chromophore constituentand the polymeric constituent are distinct parts of the same molecule.Moreover, the polymeric constituent is bound directly to a nitrogen atomon the chromophore constituent. It will further be understood thatinclusion of the polymeric constituent, as with all polymeric compounds,may produce a mixture of molecules which incorporate differentquantities of monomeric units. For example, during a typicalethoxylation process the randomness of the ethylene oxide additionresults in a mixture of oligomers with different degrees ofethoxylation. As a consequence of its ethylene oxide numberdistribution, which often follows a Poisson law, a commercial materialcontains substances with somewhat different properties. For example, inone aspect the product resulting from an ethoxylation is not a singlecompound containing five (CH₂CH₂O) units as a general structure maysuggest. Instead, the product is a mixture of several homologs whosetotal of ethylene oxide units may vary from about 2 to about 10.Industrially relevant processes will typically result in such mixtures,which may normally be used directly to provide the fabric shading dye,or less commonly may undergo a purification step.

The whitening agent chromophore constituent may be selected fromacridines, anthraquinones, azines, azos, benzodifuranes,benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines,diphenylmethanes, formazans, hemicyanines, indigoids, methanes,naphthalimides, naphthoquinones, nitros, nitrosos, oxazines,phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes,triphenylmethanes, xanthenes and mixtures thereof. Preferably, thewhitening agent is ananthraquinone or an azo dye, and even morepreferably the whitening agent is an azo dye. The chromophoreconstituent is characterized in that it emits or absorbs wavelengths toprovide a color on substrates in the range of blue, red, violet, purple,or combinations thereof upon exposure to light. Preferably, thechromophore constituent exhibits an absorbance spectrum value from about520 nanometers to about 640 nanometers in water, and more preferablyfrom about 570 nanometers to about 610 nanometers in water. Preferably,the chromophore constituent exhibits an emission spectrum value fromabout 400 nanometers to about 480 nanometers in water.

The polymeric component comprises at least two repeating glycerol units.Suitable polymeric components can be characterized by the followingstructure [(CH₂CH₂O)_(x)(CH₂C(OR)HCH₂O)_(y)(CH₂CH₂O)_(z′)H]. Each R isindependently selected from the group consisting of H, (CH₂CH₂O)_(z′)H,and mixtures thereof. The groups indicated by indices x, y and z may bearranged in any order and x=0 to 10, 1≤y≤5 and at least one y≥2.Independently each z=0 to 5 and each z′=0 to 5.

Suitable polymeric constituents may further include polyoxyalkylenechains having multiple repeating units. Preferably the polyoxyalkylenechains have from 2 to about 20 repeating units, and more preferably from2 to about 15 or even from about 3 to about 10 repeating units.Non-limiting examples of polyoxyalkylene chains include ethylene oxide,propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

Without wishing to be bound by theory, it is believed that dyesemploying polyglycerol groups as the polymeric constituent may besuperior to those using typical alkyleneoxide groups since the latterare believed to be more susceptible to having a cloud point at highertemperatures that adversely impacts the solubility and subsequentfunctioning of the dye. This is because the polyglycerol group cancontribute at least one and in some cases two strong hydrogen bondinghydroxyl moieties per glycerol monomer. Alkyleneoxide chains rely moreon the weaker hydrogen bonding afforded by the ether oxygens, with onlya single hydroxyl group at the end of the chain.

The whitening agent of the present invention may be characterized by thefollowing structure:

-   -   wherein each R⁵ is independently selected from the group        consisting of alkyl, oxyalkyl, oxyaryl, sulfonamidoalkyl,        sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl,        amidodiaryl, halogen, thioalkyl and thioaryl;    -   wherein the index a is an integer from about 0 to about 4;    -   wherein D is an aromatic or heteroaromatic group;    -   wherein R¹ is selected from the group consisting of H, alkyl,        aryl, aryl alkyl and        [(CH₂CH₂O)_(x)(CH₂C(OR)HCH₂O)_(y)(CH₂CH₂O)_(z′)H], wherein R² is        [(CH₂CH₂O)_(x)(CH₂C(OR)HCH₂O)_(y)(CH₂CH₂O)_(z′)H], wherein each        R is independently selected from the group consisting of H,        (CH₂CH₂O)_(z′)H, and mixtures thereof; wherein groups indicated        by indices x, y and z may be arranged in any order; wherein x=0        to 10, 1≤y≤5 and at least one y≥2; and wherein independently        each z=0 to 5 and each z′=0 to 5.

-   A preferred whitening agent of the present invention may be    characterized by the following structure:

wherein the index a is from 0 to 2; wherein each R is independentlyselected from the group consisting of H, (CH₂CH₂O)_(z′)H, and mixturesthereof; wherein groups indicated by indices x, y and z may be arrangedin any order; wherein x=0 to 10, 1≤y≤5 and at least one y≥2; and whereinindependently each z=0 to 5 and each z′=0 to 5.

As will be appreciated by those skilled in the art unreacted startingmaterials and additional components resulting from minor side reactionswill typically be present at levels that are unlikely to significantlyimpact the whitening agent's performance, as perceived by the averageconsumer. As will further be appreciated, when present at levels thatmay impact the whitening agent's performance, or the overall performanceof a detergent formulation containing the mixture, as perceived by theaverage consumer, such additional components may be removed or retainedas desired.

The Test Methods provided below can be used to determine if a dye, or amixture of dyes, is a whitening agent for the purposes of the presentinvention.

Test Methods

I. Method for Determining Deposition for a Dye

a.) Unbrightened Multifiber Fabric Style 41 swatches (MFF41, 5 cm×10 cm,average weight 1.46 g) serged with unbrightened thread are purchasedfrom Testfabrics, Inc. (West Pittston, Pa.). MFF41 swatches are strippedprior to use by washing two full cycles in AATCC heavy duty liquidlaundry detergent (HDL) nil brightener at 49° C. and washing 3additional full cycles at 49° C. without detergent. Four replicateswatches are placed into each flask.

b.) A sufficient volume of AATCC standard nil brightener HDL detergentsolution is prepared by dissolving the detergent in 0 gpg water at roomtemperature at a concentration of 1.55 g per liter.

c.) A concentrated stock solution of dye is prepared in an appropriatesolvent selected from dimethyl sulfoxide (DMSO), ethanol or 50:50ethanol:water. Ethanol is preferred. The dye stock is added to a beakercontaining 400 mL detergent solution (prepared in step I.b. above) in anamount sufficient to produce an aqueous solution absorbance at theλ_(max) of 0.1 AU (±0.01 AU) in a cuvette of path length 1.0 cm. For amixture of dyes, the sum of the aqueous solution absorbance at theλ_(max) of the individual dyes is 0.1 AU (±0.01 AU) in a cuvette of pathlength 1.0 cm. Total organic solvent concentration in a wash solutionfrom the concentrated stock solution is less than 0.5%. A 125 mL aliquotof the wash solution is placed into 3 separate disposable 250 mLErlenmeyer flasks (Thermo Fisher Scientific, Rochester, N.Y.). Solutionhardness is adjusted to 6 gpg by addition of an appropriate volume of10,000 gpg Ca:Mg (3:1) hardness stock solution prepared in deionizedwater.

d.) Four MFF41 swatches are placed into each flask (which correlates toapproximately a 25:1 liquor:fabric ratio), flasks are capped andmanually shaken to wet the swatches. Flasks are placed onto a Model 75wrist action shaker from Burrell Scientific, Inc. (Pittsburgh, Pa.) andagitated on the highest setting of 10 (390 oscillations per minute withan arc of 14.6°). After 12 minutes, the wash solution is removed byvacuum aspiration, 125 mL of 0 gpg water is added for a rinse, hardnessof the rinse water is adjusted to 6 gpg as noted above, and the flasksagitated for 4 additional minutes. Rinse solution is removed by vacuumaspiration and swatches are spun in a Mini Countertop Spin Dryer (TheLaundry Alternative Inc., Nashua, N.H.) for 5 minutes, after which theyare allowed to air dry in the dark.

e.) L*, a*, and b* values for the 3 most consumer relevant fabric types,cotton and polyester, are measured on the dry swatches using a LabScanXE reflectance spectrophotometer (HunterLabs, Reston, Va.; D65illumination, 10° observer, UV light excluded). The L*, a*, and b*values of the 12 swatches (3 flasks each containing 4 swatches) areaveraged and the hueing deposition (HD) of the dye is calculated foreach fabric type using the following equation:

HD=DE*=((L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²)^(1/2)

wherein the subscripts c and s respectively refer to the control, i.e.,the fabric washed in detergent with no dye, and the fabric washed indetergent containing dye, or a mixture of dyes, according to the methoddescribed above. The HD for any consumer relevant fabric, such as nylon,can be determined in the same manner.

II. Method for Determining Relative Hue Angle (vs. Nil Dye Control)

-   -   a) The a* and b* values of the 12 swatches from each solution        were averaged and the following formulas used to determine Δa*        and Δb*:

Δa*=a* _(c) −a* _(s) and Δb*=b* _(c) −b* _(s)

-   -   -   wherein the subscripts c and s respectively refer to the            fabric washed in detergent with no dye and the fabric washed            in detergent containing dye, or mixture of dyes, according            to the method described in I. above.

    -   b.) If the absolute value of both Δa* and Δb*<0.25, no Relative        Hue Angle (RHA) was calculated. If the absolute value of either        Δa* or Δb* were ≥0.25, the RHA was determined using one of the        following formulas:

When Δb*≥0, RHA=A TAN 2(Δa*,Δb*)

WhenΔb*<0,RHA=360+A TAN 2(Δa*,Δb*)

III. Method to Determine if a Dye is a Whitening Agent

A dye, or mixture of dyes, is considered a whitening agent (also knownas a hueing dye) for the purposes of the present invention if (a) eitherthe HD_(cotton) or the HD_(polyester) is greater than or equal to 2.0DE* units or preferably greater than or equal to 3.0, or 4.0 or even5.0, according to the formula above, and (b) the relative hue angle (seeMethod III. below) on the fabric that meets the DE* criterion in (a) iswithin 240 to 345, more preferably 260 to 325, even more preferably 270to 310. If the value of HD for both fabric types is less than 2.0 DE*units, or if the relative hue angle is not within the prescribed rangeon each fabric for which the DE* meets the criteria the dye is not ashading dye for the purposes of the present invention.

The whitening agent's described in the present specification may beincorporated into a laundry care composition including but not limitedto laundry detergents and fabric care compositions. Such compositionscomprise one or more of said whitening agents and a laundry careingredient. The whitening agent may be added to cellulose and othersubstrates using a variety of application techniques. For application tocellulose-containing and other textile substrates, the whitening agentis preferably included as an additive in laundry detergent. Thus,application to the textile substrate actually occurs when a consumeradds laundry detergent to a washing machine. Similarly, RAFScompositions are typically added in the rinse cycle, which is after thedetergent solution has been used and replaced with the rinsing solutionin typical laundering processes. For application to cellulosic papersubstrates, the whitening agent may be added to the paper pulp mixtureprior to formation of the final paper product.

The laundry care compositions including laundry detergents may be insolid or liquid form, including a gel form. The laundry carecompositions including laundry detergents may also be in a unit dosepouch. The laundry detergent composition comprises a surfactant in anamount sufficient to provide desired cleaning properties.

The whitening agent may be present in the laundry detergent compositionin an amount from about 0.0001% to about 10% by weight of thecomposition, more preferably from about 0.0001% to about 5% by weight ofthe composition, and even more preferably from about 0.0001% to about 1%by weight of the composition.

The laundry detergent composition comprises a surfactant in an amountsufficient to provide desired cleaning properties. In one embodiment,the laundry detergent composition comprises, by weight, from about 5% toabout 90% of the surfactant, and more specifically from about 5% toabout 70% of the surfactant, and even more specifically from about 5% toabout 40%. The surfactant may comprise anionic, nonionic, cationic,zwitterionic and/or amphoteric surfactants. In a more specificembodiment, the detergent composition comprises anionic surfactant,nonionic surfactant, or mixtures thereof.

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C₁₀₋₁₆ alkylbenzene sulfonic acids, preferably C₁₁₋₁₄ alkyl benzene sulfonic acids.Preferably the alkyl group is linear and such linear alkyl benzenesulfonates are known as “LAS”. Alkyl benzene sulfonates, andparticularly LAS, are well known in the art. Such surfactants and theirpreparation are described for example in U.S. Pat. Nos. 2,220,099 and2,477,383. Especially preferred are the sodium and potassium linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄,e.g., C₁₂, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In a specificembodiment, R′ is C₁₀-C₁₈ alkyl, n is from about 1 to 15, and M issodium, potassium, ammonium, alkylammonium, or alkanolammonium. In morespecific embodiments, R′ is a C₁₂-C₁₆, n is from about 1 to 6 or evenfrom about 1 to 3 or from about 1 to 1.5 and M is sodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoxylated, e.g., non-ethoxylated,alkyl ether sulfate surfactants are those produced by the sulfation ofhigher C₈-C₂₀ fatty alcohols. Conventional primary alkyl sulfatesurfactants have the general formula: ROSO₃-M⁺ wherein R is typically alinear C₈-C₂₀ hydrocarbyl group, which may be straight chain or branchedchain, and M is a water-solubilizing cation. In specific embodiments, Ris a C₁₀-C₁₅ alkyl, and M is alkali metal, more specifically R isC₁₂-C₁₄ and M is sodium.

Specific, non-limiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS); c) C₁₀-C₁₈ secondary(2,3) alkyl sulfates; d) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) whereinpreferably x is from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylatespreferably comprising 1-5 ethoxy units; f) mid-chain branched alkylsulfates as discussed in U.S. Pat. Nos. 6,020,303 and 6,060,443; g)mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat. Nos.6,008,181 and 6,020,303; h) modified alkylbenzene sulfonate (MLAS) asdiscussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; i)methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. Preferred for use in the liquid detergent productsherein are those nonionic surfactants which are normally liquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.Preferably R¹ is an alkyl group, which may be primary or secondary, thatcomprises from about 9 to 15 carbon atoms, more preferably from about 10to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcoholswill also be ethoxylated materials that contain from about 2 to 12ethylene oxide moieties per molecule, more preferably from about 3 to 10or even from about 7 to 9 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17. More preferably, the HLBof this material will range from about 6 to 15, most preferably fromabout 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have beenmarketed under the tradenames Neodol and Dobanol by the Shell ChemicalCompany.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20,preferably from 10 to 16 carbon atoms, and is more preferably C₁₂-C₁₆primary alkyl. R′ is a short-chain moiety, preferably selected fromhydrogen, methyl and —CH₂OH. When x+y+z is different from 0, EO isethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxidesurfactants are illustrated by C₁₂₋₁₄ alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x if from 1-30, as discussed in U.S.Pat. Nos. 6,153,577, 6,020,303 and 6,093,856; f) Alkylpolysaccharides asdiscussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 26, 1986;specifically alkylpolyglycosides as discussed in U.S. Pat. Nos.4,483,780 and 4,483,779; g) Polyhydroxy fatty acid amides as discussedin U.S. Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, andWO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactantsas discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30. In general compositions with increasing weight ratiosfavoring nonionic surfactants may lead to increased deposition of theinventive whitening agents in a wash. Such factors must always becarefully weighed over against any risk elements that may also increasein these formulations. The ordinarily-skilled artisan is well aware ofsuch factors and formulates accordingly.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (preferably C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate wherethe alkyl group can be C₈ to C₁₈, preferably C₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents comprises at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one comprises an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

As noted, the compositions may be in the form of a solid, either intablet or particulate form, including, but not limited to particles,flakes, or the like, or the compositions may be in the form of a liquid.The liquid detergent compositions comprise an aqueous, non-surfaceactive liquid carrier. Generally, the amount of the aqueous, non-surfaceactive liquid carrier employed in the compositions herein will beeffective to solubilize, suspend or disperse the composition components.For example, the compositions may comprise, by weight, from about 5% toabout 90%, more specifically from about 10% to about 70%, and even morespecifically from about 20% to about 70% of the aqueous, non-surfaceactive liquid carrier.

The most cost effective type of aqueous, non-surface active liquidcarrier is, of course, water itself. Accordingly, the aqueous,non-surface active liquid carrier component will generally be mostly, ifnot completely, comprised of water. While other types of water-miscibleliquids, such alkanols, diols, other polyols, ethers, amines, and thelike, have been conventionally been added to liquid detergentcompositions as co-solvents or stabilizers, for purposes of the presentinvention, the utilization of such water-miscible liquids should beminimized to hold down composition cost. Accordingly, the aqueous liquidcarrier component of the liquid detergent products herein will generallycomprise water present in concentrations ranging from about 5% to about90%, more preferably from about 20% to about 70%, by weight of thecomposition.

Detergent compositions may also contain bleaching agents. Suitablebleaching agents include, for example, hydrogen peroxide sources, suchas those described in detail in the herein incorporated Kirk Othmer'sEncyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons),Vol. 4, pp. 271-300 “Bleaching Agents (Survey).” These hydrogen peroxidesources include the various forms of sodium perborate and sodiumpercarbonate, including various coated and modified forms of thesecompounds.

The preferred source of hydrogen peroxide used herein can be anyconvenient source, including hydrogen peroxide itself. For example,perborate, e.g., sodium perborate (any hydrate but preferably the mono-or tetra-hydrate), sodium carbonate peroxyhydrate or equivalentpercarbonate salts, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Mixtures of any convenienthydrogen peroxide sources can also be used.

A suitable percarbonate bleach comprises dry particles having an averageparticle size in the range from about 500 micrometers to about 1,000micrometers, not more than about 10% by weight of said particles beingsmaller than about 200 micrometers and not more than about 10% by weightof said particles being larger than about 1,250 micrometers. Optionally,the percarbonate can be coated with a silicate, borate or water-solublesurfactants. Percarbonate is available from various commercial sourcessuch as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also comprise as the bleachingagent a chlorine-type bleaching material. Such agents are well known inthe art, and include for example sodium dichloroisocyanurate (“NaDCC”).However, chlorine-type bleaches are less preferred for compositionswhich comprise enzymes.

(a) Bleach Activators—

Preferably, the peroxygen bleach component in the composition isformulated with an activator (peracid precursor). The activator ispresent at levels of from about 0.01%, preferably from about 0.5%, morepreferably from about 1% to about 15%, preferably to about 10%, morepreferably to about 8%, by weight of the composition. A bleach activatoras used herein is any compound which, when used in conjunction with ahydrogen peroxide, source leads to the in situ production of the peracidcorresponding to the bleach activator. Various non-limiting examples ofactivators are disclosed in U.S. Pat. Nos. 5,576,282; 4,915,854 and4,412,934. See also U.S. Pat. No. 4,634,551 for other typical bleachesand activators useful herein.

Preferred activators are selected from the group consisting oftetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C₁₀—OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈—OBS),perhydrolyzable esters and mixtures thereof, most preferablybenzoylcaprolactam and benzoylvalerolactam. Particularly preferredbleach activators in the pH range from about 8 to about 11 are thoseselected having an OBS or VL leaving group. Preferred hydrophobic bleachactivators include, but are not limited to,nonanoyloxybenzene-sulphonate (NOBS); 4-[N-(nonanoyl) aminohexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an example ofwhich is described in U.S. Pat. No. 5,523,434;dodecanoyloxybenzenesulphonate (LOBS or C₁₂-OBS);10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁—OBS with unsaturation inthe 10 position); and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in U.S. Pat. No.5,998,350 to Burns et al.; U.S. Pat. No. 5,698,504 to Christie et al.;U.S. Pat. No. 5,695,679 to Christie et al.; U.S. Pat. No. 5,686,401 toWilley et al.; U.S. Pat. No. 5,686,014 to Hartshorn et al.; U.S. Pat.No. 5,405,412 to Willey et al.; U.S. Pat. No. 5,405,413 to Willey etal.; U.S. Pat. No. 5,130,045 to Mitchel et al.; and U.S. Pat. No.4,412,934 to Chung et al., and patent application Ser. No. 08/064,564,all of which are incorporated herein by reference.

The mole ratio of peroxygen source (as AvO) to bleach activator in thepresent invention generally ranges from at least 1:1, preferably fromabout 20:1, more preferably from about 10:1 to about 1:1, preferably toabout 3:1.

Quaternary substituted bleach activators may also be included. Thepresent laundry compositions preferably comprise a quaternarysubstituted bleach activator (QSBA) or a quaternary substituted peracid(QSP, preferably a quaternary substituted percarboxylic acid or aquaternary substituted peroxyimidic acid); more preferably, the former.Preferred QSBA structures are further described in U.S. Pat. No.5,686,015 to Willey et al.; U.S. Pat. No. 5,654,421 to Taylor et al.;U.S. Pat. No. 5,460,747 to Gosselink et al.; U.S. Pat. No. 5,584,888 toMiracle et al.; U.S. Pat. No. 5,578,136 to Taylor et al.; all of whichare incorporated herein by reference.

Highly preferred bleach activators useful herein are amide-substitutedas described in U.S. Pat. Nos. 5,698,504; 5,695,679; and 5,686,014, eachof which are cited herein above. Preferred examples of such bleachactivators include: (6-octanamidocaproyl) oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

Other useful activators are disclosed in U.S. Pat. Nos. 5,698,504;5,695,679; and 5,686,014, each of which is cited herein above, and inU.S. Pat. No. 4,966,723 to Hodge et al. These activators includebenzoxazin-type activators, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)=N—.

Nitriles, such as acetonitriles and/or ammonium nitriles and otherquaternary nitrogen containing nitriles, are another class of activatorsthat are useful herein. Non-limiting examples of such nitrile bleachactivators are described in U.S. Pat. Nos. 6,133,216; 3,986,972;6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327;5,004,558; and in EP Nos. 790 244, 775 127, 1 017 773, 1 017 776; and inWO 99/14302, WO 99/14296, WO96/40661, all of which are incorporatedherein by reference.

Depending on the activator and precise application, good bleachingresults can be obtained from bleaching systems having an in-use pH offrom about 6 to about 13, and preferably from about 9.0 to about 10.5.Typically, for example, activators with electron-withdrawing moietiesare used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

Acyl lactam activators, as described in U.S. Pat. Nos. 5,698,504;5,695,679 and 5,686,014, each of which is cited herein above, are veryuseful herein, especially the acyl caprolactams (see for example WO94-28102 A) and acyl valerolactams (see U.S. Pat. No. 5,503,639 toWilley et al. incorporated herein by reference).

(b) Organic Peroxides, Especially Diacyl Peroxides—

These are extensively illustrated in Kirk Othmer, Encyclopedia ofChemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90and especially at pages 63-72, all incorporated herein by reference. Ifa diacyl peroxide is used, it will preferably be one which exertsminimal adverse impact on fabric care, including color care.

(c) Metal-Containing Bleach Catalysts—

The compositions and methods of the present invention can alsooptionally include metal-containing bleach catalysts, preferablymanganese and cobalt-containing bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity (such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations), an auxiliary metal cation havinglittle or no bleach catalytic activity (such as zinc or aluminumcations), and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243 to Bragg.

Manganese Metal Complexes—

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416;and 5,114,606; and European Pat. App. Pub. Nos. 549,271 A1; 549,272 A1;544,440 A2; and 544,490 A1. Preferred examples of these catalystsinclude Mn^(IV) ₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂,Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following: U.S. Pat. Nos. 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Cobalt Metal Complexes—

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936; 5,595,967; and 5,703,030; and M.L. Tobe, “Base Hydrolysis of Transition-Metal Complexes”, Adv. Inorg.Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobaltcatalyst useful herein are cobalt pentaamine acetate salts having theformula [Co(NH₃)₅OAc] T_(y), wherein “OAc” represents an acetate moietyand “T_(y)” is an anion, and especially cobalt pentaamine acetatechloride, [Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂;[Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc](SO₄); [Co—(NH₃)₅OAc](BF₄)₂; and[Co(NH₃)₅OAc](NO₃)₂(herein “PAC”).

These cobalt catalysts are readily prepared by known procedures, such astaught for example in U.S. Pat. Nos. 6,302,921; 6,287,580; 6,140,294;5,597,936; 5,595,967; and 5,703,030; in the Tobe article and thereferences cited therein; and in U.S. Pat. No. 4,810,410; J. Chem. Ed.(1989), 66 (12), 1043-45; The Synthesis and Characterization ofInorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982);Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960);and Journal of Physical Chemistry, 56, 22-25 (1952).

Transition Metal Complexes of Macropolycyclic Rigid Ligands—

Compositions herein may also suitably include as bleach catalyst atransition metal complex of a macropolycyclic rigid ligand. The amountused is a catalytically effective amount, suitably about 1 ppb or more,for example up to about 99.9%, more typically about 0.001 ppm or more,preferably from about 0.05 ppm to about 500 ppm (wherein “ppb” denotesparts per billion by weight and “ppm” denotes parts per million byweight).

Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which aresuitable for use in the invention compositions can in general includeknown compounds where they conform with the definition herein, as wellas, more preferably, any of a large number of novel compounds expresslydesigned for the present laundry or laundry uses, and are non-limitinglyillustrated by any of the following:

-   Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane    Manganese(II)-   Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)    Hexafluorophosphate-   Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)    Hexafluorophosphate-   Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane    Manganese(III) Hexafluorophosphate-   Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)    Tetrafluoroborate-   Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane    Manganese(III) Hexafluorophosphate-   Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III)    Hexafluorophosphate-   Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)-   Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane    Manganese(II)-   Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane    Manganese(II).

As a practical matter, and not by way of limitation, the compositionsand methods herein can be adjusted to provide on the order of at leastone part per hundred million of the active bleach catalyst species inthe composition comprising a lipophilic fluid and a bleach system, andwill preferably provide from about 0.01 ppm to about 25 ppm, morepreferably from about 0.05 ppm to about 10 ppm, and most preferably fromabout 0.1 ppm to about 5 ppm, of the bleach catalyst species in thecomposition comprising a lipophilic fluid and a bleach system.

(d) Bleach Boosting Compounds—

The compositions herein may comprise one or more bleach boostingcompounds. Bleach boosting compounds provide increased bleachingeffectiveness in lower temperature applications. The bleach boosters actin conjunction with conventional peroxygen bleaching sources to provideincreased bleaching effectiveness. This is normally accomplished throughin situ formation of an active oxygen transfer agent such as adioxirane, an oxaziridine, or an oxaziridinium. Alternatively, preformeddioxiranes, oxaziridines and oxaziridiniums may be used.

Among suitable bleach boosting compounds for use in accordance with thepresent invention are cationic imines, zwitterionic imines, anionicimines and/or polyionic imines having a net charge of from about +3 toabout −3, and mixtures thereof. These imine bleach boosting compounds ofthe present invention include those of the general structure:

-   -   where R¹-R⁴ may be a hydrogen or an unsubstituted or substituted        radical selected from the group consisting of phenyl, aryl,        heterocyclic ring, alkyl and cycloalkyl radicals.

Among preferred bleach boosting compounds are zwitterionic bleachboosters, which are described in U.S. Pat. Nos. 5,576,282 and 5,718,614.Other bleach boosting compounds include cationic bleach boostersdescribed in U.S. Pat. Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826;5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen sourceemployed in the present invention may comprise any of these well knownsources, including peroxygen compounds as well as compounds, which underconsumer use conditions, provide an effective amount of peroxygen insitu. The peroxygen source may include a hydrogen peroxide source, thein situ formation of a peracid anion through the reaction of a hydrogenperoxide source and a bleach activator, preformed peracid compounds ormixtures of suitable peroxygen sources. Of course, one of ordinary skillin the art will recognize that other sources of peroxygen may beemployed without departing from the scope of the invention. The bleachboosting compounds, when present, are preferably employed in conjunctionwith a peroxygen source in the bleaching systems of the presentinvention.

(e) Preformed Peracids—

Also suitable as bleaching agents are preformed peracids. The preformedperacid compound as used herein is any convenient compound which isstable and which under consumer use conditions provides an effectiveamount of peracid or peracid anion. The preformed peracid compound maybe selected from the group consisting of percarboxylic acids and salts,percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, and mixtures thereof. Examples ofthese compounds are described in U.S. Pat. No. 5,576,282 to Miracle etal.

One class of suitable organic peroxycarboxylic acids have the generalformula:

-   -   wherein R is an alkylene or substituted alkylene group        containing from 1 to about 22 carbon atoms or a phenylene or        substituted phenylene group, and Y is hydrogen, halogen, alkyl,        aryl, —C(O)OH or —C(O)OOH.

Organic peroxyacids suitable for use in the present invention cancontain either one or two peroxy groups and can be either aliphatic oraromatic. When the organic peroxycarboxylic acid is aliphatic, theunsubstituted peracid has the general formula:

-   -   wherein Y can be, for example, H, CH₃, CH₂Cl, C(O)OH, or        C(O)OOH; and n is an integer from 0 to 20. When the organic        peroxycarboxylic acid is aromatic, the unsubstituted peracid has        the general formula:

-   -   wherein Y can be, for example, hydrogen, alkyl, alkylhalogen,        halogen, C(O)OH or C(O)OOH.

Typical monoperoxy acids useful herein include alkyl and arylperoxyacids such as:

-   -   (i) peroxybenzoic acid and ring-substituted peroxybenzoic acid,        e.g. peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium        salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid        (sodium salt);    -   (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy        acids, e.g. peroxylauric acid, peroxystearic acid,        N-nonanoylaminoperoxycaproic acid (NAPCA),        N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and        N,N-phthaloylaminoperoxycaproic acid (PAP);    -   (iii) amidoperoxyacids, e.g. monononylamide of either        peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).

Typical diperoxyacids useful herein include alkyl diperoxyacids andaryldiperoxyacids, such as:

-   -   (i) 1,12-diperoxydodecanedioic acid;    -   (ii) 1,9-diperoxyazelaic acid;    -   (iii) diperoxybrassylic acid; diperoxysebacic acid and        diperoxyisophthalic acid;    -   (iv) 2-decyldiperoxybutane-1,4-dioic acid;    -   (v) 4,4′-sulfonylbisperoxybenzoic acid.

Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781 toHartman and U.S. Pat. No. 4,634,551 to Burns et al.; European PatentApplication 0,133,354 to Banks et al.; and U.S. Pat. No. 4,412,934 toChung et al. Sources also include 6-nonylamino-6-oxoperoxycaproic acidas described in U.S. Pat. No. 4,634,551 to Burns et al. Persulfatecompounds such as for example OXONE, manufactured commercially by E.I.DuPont de Nemours of Wilmington, Del. can also be employed as a suitablesource of peroxymonosulfuric acid. PAP is disclosed in, for example,U.S. Pat. Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431.

(f) Photobleaches—

Suitable photobleaches for use in the treating compositions of thepresent invention include, but are not limited to, the photobleachesdescribed in U.S. Pat. Nos. 4,217,105 and 5,916,481.

(g) Enzyme Bleaching—

Enzymatic systems may be used as bleaching agents. The hydrogen peroxidemay also be present by adding an enzymatic system (i.e. an enzyme and asubstrate therefore) which is capable of generating hydrogen peroxide atthe beginning or during the washing and/or rinsing process. Suchenzymatic systems are disclosed in EP Patent Application 91202655.6filed Oct. 9, 1991.

The present invention compositions and methods may utilize alternativebleach systems such as ozone, chlorine dioxide and the like. Bleachingwith ozone may be accomplished by introducing ozone-containing gashaving ozone content from about 20 to about 300 g/m³ into the solutionthat is to contact the fabrics. The gas:liquid ratio in the solutionshould be maintained from about 1:2.5 to about 1:6. U.S. Pat. No.5,346,588 describes a process for the utilization of ozone as analternative to conventional bleach systems and is herein incorporated byreference.

The detergent compositions of the present invention may also include anynumber of additional optional ingredients. These include conventionallaundry detergent composition components such as non-tinting dyes,detersive builders, enzymes, enzyme stabilizers (such as propyleneglycol, boric acid and/or borax), suds suppressors, soil suspendingagents, soil release agents, other fabric care benefit agents, pHadjusting agents, chelating agents, smectite clays, solvents,hydrotropes and phase stabilizers, structuring agents, dye transferinhibiting agents, opacifying agents, optical brighteners, perfumes andcoloring agents. The various optional detergent composition ingredients,if present in the compositions herein, should be utilized atconcentrations conventionally employed to bring about their desiredcontribution to the composition or the laundering operation. Frequently,the total amount of such optional detergent composition ingredients canrange from about 0.01% to about 50%, more preferably from about 0.1% toabout 30%, by weight of the composition.

The liquid detergent compositions are in the form of an aqueous solutionor uniform dispersion or suspension of surfactant, whitening agent, andcertain optional other ingredients, some of which may normally be insolid form, that have been combined with the normally liquid componentsof the composition, such as the liquid alcohol ethoxylate nonionic, theaqueous liquid carrier, and any other normally liquid optionalingredients. Such a solution, dispersion or suspension will beacceptably phase stable and will typically have a viscosity which rangesfrom about 100 to 600 cps, more preferably from about 150 to 400 cps.For purposes of this invention, viscosity is measured with a BrookfieldLVDV-II+ viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stableliquid detergent composition. In a preferred process for preparing suchcompositions, a liquid matrix is formed containing at least a majorproportion, and preferably substantially all, of the liquid components,e.g., nonionic surfactant, the non-surface active liquid carriers andother optional liquid components, with the liquid components beingthoroughly admixed by imparting shear agitation to this liquidcombination. For example, rapid stirring with a mechanical stirrer mayusefully be employed. While shear agitation is maintained, substantiallyall of any anionic surfactants and the solid form ingredients can beadded. Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills, are incorporated. As a variation of the composition preparationprocedure hereinbefore described, one or more of the solid componentsmay be added to the agitated mixture as a solution or slurry ofparticles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In an alternate embodiment for forming the liquid detergentcompositions, the whitening agent is first combined with one or moreliquid components to form a whitening agent premix, and this whiteningagent premix is added to a composition formulation containing asubstantial portion, for example more than 50% by weight, morespecifically, more than 70% by weight, and yet more specifically, morethan 90% by weight, of the balance of components of the laundrydetergent composition. For example, in the methodology described above,both the whitening agent premix and the enzyme component are added at afinal stage of component additions. In a further embodiment, thewhitening agent is encapsulated prior to addition to the detergentcomposition, the encapsulated whitening agent is suspended in astructured liquid, and the suspension is added to a compositionformulation containing a substantial portion of the balance ofcomponents of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form.Suitable solid forms include tablets and particulate forms, for example,granular particles or flakes. Various techniques for forming detergentcompositions in such solid forms are well known in the art and may beused herein. In one embodiment, for example when the composition is inthe form of a granular particle, the whitening agent is provided inparticulate form, optionally including additional but not all componentsof the laundry detergent composition. The whitening agent particulate iscombined with one or more additional particulates containing a balanceof components of the laundry detergent composition. Further, thewhitening agent, optionally including additional but not all componentsof the laundry detergent composition, may be provided in an encapsulatedform, and the whitening agent encapsulate is combined with particulatescontaining a substantial balance of components of the laundry detergentcomposition.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingof fabrics. Generally, an effective amount of such compositions is addedto water, preferably in a conventional fabric laundering automaticwashing machine, to form such aqueous laundering solutions. The aqueouswashing solution so formed is then contacted, preferably underagitation, with the fabrics to be laundered therewith. An effectiveamount of the liquid detergent compositions herein added to water toform aqueous laundering solutions can comprise amounts sufficient toform from about 500 to 7,000 ppm of composition in aqueous washingsolution. More preferably, from about 1,000 to 3,000 ppm of thedetergent compositions herein will be provided in aqueous washingsolution.

Fabric Care Compositions/Rinse Added Fabric Softening Compositions

In another specific embodiment, the whitening agents of the presentinvention may be included in a fabric care composition. The fabric carecomposition may be comprised of at least one whitening agent and a rinseadded fabric softening composition (“RAFS;” also known as rinse addedfabric conditioning compositions). Examples of typical rinse addedsoftening compositions can be found in U.S. Provisional PatentApplication Ser. No. 60/687,582 filed on Oct. 8, 2004. The rinse addedfabric softening compositions of the present invention may comprise (a)fabric softening active and (b) a thiazolium dye. The rinse added fabricsoftening composition may comprise from about 1% to about 90% by weightof the FSA, more preferably from about 5% to about 50% by weight of theFSA. The whitening agent may be present in the rinse added fabricsoftening composition in an amount from about 0.5 ppb to about 50 ppm,more preferably from about 0.5 ppm to about 30 ppm.

In one embodiment of the invention, the fabric softening active(hereinafter “FSA”) is a quaternary ammonium compound suitable forsoftening fabric in a rinse step. In one embodiment, the FSA is formedfrom a reaction product of a fatty acid and an aminoalcohol obtainingmixtures of mono-, di-, and, in one embodiment, triester compounds. Inanother embodiment, the FSA comprises one or more softener quaternaryammonium compounds such, but not limited to, as a monoalkyquaternaryammonium compound, a diamido quaternary compound and a diesterquaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternaryammonium (hereinafter “DQA”) compound composition. In certainembodiments of the present invention, the DQA compounds compositionsalso encompasses a description of diamido FSAs and FSAs with mixed amidoand ester linkages as well as the aforementioned diester linkages, allherein referred to as DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA in the present CFSCincludes a compound comprising the formula:

{R _(4-m) −N ⁺−[(CH ₂)_(n) −Y−R ¹]_(m) }X ⁻

-   -   wherein each R substituent is either hydrogen, a short chain        C₁-C₆, preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl (most preferred), ethyl, propyl, hydroxyethyl, and the        like, poly (C₂₋₃ alkoxy), preferably polyethoxy, group, benzyl,        or mixtures thereof; each m is 2 or 3; each n is from 1 to about        4, preferably 2; each Y is —O—(O)C—, —C(O)—O—, —NR—C(O)—, or        —C(O)—NR—and it is acceptable for each Y to be the same or        different; the sum of carbons in each R¹, plus one when Y is        —O—(O)C— or —NR—C(O)—, is C₁₂-C₂₂, preferably C₁₄-C₂₀, with each        R¹ being a hydrocarbyl, or substituted hydrocarbyl group; it is        acceptable for R¹ to be unsaturated or saturated and branched or        linear and preferably it is linear; it is acceptable for each R¹        to be the same or different and preferably these are the same;        and X⁻ can be any softener-compatible anion, preferably,        chloride, bromide, methylsulfate, ethylsulfate, sulfate,        phosphate, and nitrate, more preferably chloride or methyl        sulfate. Preferred DQA compounds are typically made by reacting        alkanolamines such as MDEA (methyldiethanolamine) and TEA        (triethanolamine) with fatty acids. Some materials that        typically result from such reactions include        N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or        N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium        methylsulfate wherein the acyl group is derived from animal        fats, unsaturated, and polyunsaturated, fatty acids, e.g.,        tallow, hardended tallow, oleic acid, and/or partially        hydrogenated fatty acids, derived from vegetable oils and/or        partially hydrogenated vegetable oils, such as, canola oil,        safflower oil, peanut oil, sunflower oil, corn oil, soybean oil,        tall oil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in U.S. Pat.No. 5,759,990 at column 4, lines 45-66. In one embodiment, the FSAcomprises other actives in addition to DQA (1) or DQA. In yet anotherembodiment, the FSA comprises only DQA (1) or DQA and is free oressentially free of any other quaternary ammonium compounds or otheractives. In yet another embodiment, the FSA comprises the precursoramine that is used to produce the DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:

[R_(4-m)—N⁽⁺⁾—R¹ _(m)]A⁻

-   -   wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, preferably        C₁₄-C₂₀, but no more than one being less than about C₁₂ and then        the other is at least about 16, hydrocarbyl, or substituted        hydrocarbyl substituent, preferably C₁₀-C₂₀ alkyl or alkenyl        (unsaturated alkyl, including polyunsaturated alkyl, also        referred to sometimes as “alkylene”), most preferably C₁₂-C₁₈        alkyl or alkenyl, and branch or unbranched. In one embodiment,        the Iodine Value (IV) of the FSA is from about 1 to 70; each R        is H or a short chain C₁-C₆, preferably C₁-C₃ alkyl or        hydroxyalkyl group, e.g., methyl (most preferred), ethyl,        propyl, hydroxyethyl, and the like, benzyl, or (R²O)₂₋₄H where        each R² is a C₁₋₆ alkylene group; and A⁻ is a softener        compatible anion, preferably, chloride, bromide, methylsulfate,        ethylsulfate, sulfate, phosphate, or nitrate; more preferably        chloride or methyl sulfate.

Examples of these FSAs include dialkydimethylammonium salts anddialkylenedimethylammonium salts such as ditallowdimethylammonium andditallowdimethylammonium methylsulfate. Examples of commerciallyavailable dialkylenedimethylammonium salts usable in the presentinvention are di-hydrogenated tallow dimethyl ammonium chloride andditallowdimethyl ammonium chloride available from Degussa under thetrade names Adogen® 442 and Adogen® 470 respectively. In one embodiment,the FSA comprises other actives in addition to DTTMAC. In yet anotherembodiment, the FSA comprises only compounds of the DTTMAC and is freeor essentially free of any other quaternary ammonium compounds or otheractives.

In one embodiment, the FSA comprises an FSA described in U.S. Pat. Pub.No. 2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79. In another embodiment, the FSA is one described inU.S. Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith etal., on paragraphs 26-31; or U.S. Pat. No. 6,494,920, at column 1, line51 et seq. detailing an “esterquat” or a quaternized fatty acidtriethanolamine ester salt.

In one embodiment, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one embodiment, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.Another specific embodiment of the invention provides for a rinse addedfabric softening composition further comprising a cationic starch.Cationic starches are disclosed in US 2004/0204337 A1. In oneembodiment, the rinse added fabric softening composition comprises fromabout 0.1% to about 7% of cationic starch by weight of the fabricsoftening composition. In one embodiment, the cationic starch is HCP401from National Starch.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, thenon-limiting list of laundry care ingredients illustrated hereinafterare suitable for use in the laundry care compositions and may bedesirably incorporated in certain embodiments of the invention, forexample to assist or enhance performance, for treatment of the substrateto be cleaned, or to modify the aesthetics of the composition as is thecase with perfumes, colorants, dyes or the like. For example, to obtainother aesthetic colors in a detergent, the present dyes may be mixedwith additional dyes or colorants, such as with a blue triphenylmethanedye. It is understood that such ingredients are in addition to thecomponents that were previously listed for any particular embodiment.The total amount of such adjuncts may range from about 0.1% to about50%, or even from about 1% to about 30%, by weight of the laundry carecomposition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable laundry care ingredients include, but are not limited to,polymers, for example cationic polymers, surfactants, builders,chelating agents, dye transfer inhibiting agents, dispersants, enzymes,and enzyme stabilizers, catalytic materials, bleach activators,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfume and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. In addition tothe disclosure below, suitable examples of such other adjuncts andlevels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and6,326,348 B1 that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants'laundry care compositions. Thus, certain embodiments of Applicants'compositions do not contain one or more of the following adjunctsmaterials: bleach activators, surfactants, builders, chelating agents,dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic metal complexes, polymeric dispersing agents,clay and soil removal/anti-redeposition agents, brighteners, sudssuppressors, dyes, additional perfumes and perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,processing aids and/or pigments. However, when one or more adjuncts arepresent, such one or more adjuncts may be present as detailed below:

Surfactants—The compositions according to the present invention cancomprise a surfactant or surfactant system wherein the surfactant can beselected from nonionic and/or anionic and/or cationic surfactants and/orampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.The surfactant is typically present at a level of from about 0.1%, fromabout 1%, or even from about 5% by weight of the cleaning compositionsto about 99.9%, to about 80%, to about 35%, or even to about 30% byweight of the cleaning compositions.

Builders—The compositions of the present invention can comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder, or fromabout 5% or 10% to about 80%, 50%, or even 30% by weight, of saidbuilder. Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds. ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The compositions herein may also optionally contain oneor more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The compositions of the present inventionmay also include one or more dye transfer inhibiting agents. Suitablepolymeric dye transfer inhibiting agents include, but are not limitedto, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acid maycomprise at least two carboxyl radicals separated from each other by notmore than two carbon atoms.

Enzymes—The compositions can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and amylases, or mixtures thereof. A typicalcombination is a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

Enzyme Stabilizers—Enzymes for use in compositions, for example,detergents can be stabilized by various techniques. The enzymes employedherein can be stabilized by the presence of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions that providesuch ions to the enzymes.

Catalytic Metal Complexes—Applicants' compositions may include catalyticmetal complexes. One type of metal-containing bleach catalyst is acatalyst system comprising a transition metal cation of defined bleachcatalytic activity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methyl-enephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobaltcatalysts are readily prepared by known procedures, such as taught forexample in U.S. Pat. Nos. 5,597,936, and 5,595,967.

Compositions herein may also suitably include a transition metal complexof a macropolycyclic rigid ligand—abbreviated as “MRL”. As a practicalmatter, and not by way of limitation, the compositions and cleaningprocesses herein can be adjusted to provide on the order of at least onepart per hundred million of the benefit agent MRL species in the aqueouswashing medium, and may provide from about 0.005 ppm to about 25 ppm,from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about5 ppm, of the MRL in the wash liquor.

Preferred transition-metals in the instant transition-metal bleachcatalyst include manganese, iron and chromium. Preferred MRL's hereinare a special type of ultra-rigid ligand that is cross-bridged such as5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane.

Suitable transition metal MRLs are readily prepared by known procedures,such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

Exemplary Detergent Formulations

Table 1 provides examples of liquid detergent formulations which includeat least one whitening agent of the present invention.

TABLE 1 Liquid Detergent Formulations Comprising the Present WhiteningAgent 1a 1b 1c 1d 1e 1f ⁴ Ingredient wt % wt % wt % wt % wt % wt %sodium alkyl ether sulfate  14.4%  14.4% 9.2%  5.4% linear alkylbenzenesulfonic  4.4%  4.4%  12.2% 5.7%  1.3%  22.0% acid alkyl ethoxylate 2.2%  2.2%  8.8% 8.1%  3.4%  18.0% amine oxide  0.7%  0.7%  1.5% citricacid  2.0%  2.0%  3.4% 1.9%  1.0%  1.6% fatty acid  3.0%  3.0%  8.3% 16.0% protease  1.0%  1.0%  0.7% 1.0%  2.5% amylase  0.2%  0.2%  0.2% 0.3% lipase 0.2% borax  1.5%  1.5%  2.4% 2.9% calcium and sodiumformate  0.2%  0.2% formic acid  1.1% amine ethoxylate polymers  1.8% 1.8%  2.1%  3.2% sodium polyacrylate  0.2% sodium polyacrylatecopolymer 0.6% DTPA¹  0.1%  0.1%  0.9% DTPMP²  0.3% EDTA³  0.1%fluorescent whitening agent  0.15%  0.15%  0.2% 0.12%   0.12%  0.2%ethanol  2.5%  2.5%  1.4% 1.5% propanediol  6.6%  6.6%  4.9% 4.0%  15.7%sorbitol 4.0% ethanolamine  1.5%  1.5%  0.8% 0.1%  11.0% sodiumhydroxide  3.0%  3.0%  4.9% 1.9%  1.0% sodium cumene sulfonate  2.0%silicone suds suppressor  0.01% perfume  0.3%  0.3%  0.7% 0.3%  0.4% 0.6% Whitening Agent 0.013% 0.001% 0.005% 0.003%  0.0005% 0.001% waterbalance balance balance balance balance balance 100.0% 100.0% 100.0%100.0%  100.0% 100.0% ¹diethylenetriaminepentaacetic acid, sodium salt²diethylenetriaminepentakismethylenephosphonic acid, sodium salt³ethylenediaminetetraacetic acid, sodium salt ⁴ a compact formula,packaged as a unitized dose in polyvinyl alcohol film

Granular Detergent Formulations

Table 2 provides examples of granular detergent formulations whichinclude at least one whitening agent of the present invention.

TABLE 2 Granular Detergent Formulations Comprising the Present WhiteningAgent 2a 2b 2c 2d 2e Ingredient wt % wt % wt % wt % wt % Na linearalkylbenzene sulfonate 3.4% 3.3% 11.0% 3.4% 3.3% Na alkylsulfate 4.0%4.1% 4.0% 4.1% Na alkyl sulfate (branched) 9.4% 9.6% 9.4% 9.6% alkylethoxylate 3.5% type A zeolite 37.4% 35.4% 26.8% 37.4% 35.4% sodiumcarbonate 22.3% 22.5% 35.9% 22.3% 22.5% sodium sulfate 1.0% 18.8% 1.0%sodium silicate 2.2% protease 0.1% 0.2% 0.1% 0.2% sodium polyacrylate1.0% 1.2% 0.7% 1.0% 1.2% carboxymethylcellulose 0.1% PEG 600 0.5% 0.5%PEG 4000 2.2% 2.2% DTPA 0.7% 0.6% 0.7% 0.6% fluorescent whitening agent0.1% 0.1% 0.1% 0.1% 0.1% sodium percarbonate 5.0% 5.0% sodiumnonanoyloxybenzenesulfonate 5.3% 5.3% silicone suds suppressor 0.02%0.02% 0.02% 0.02% perfume 0.3% 0.3% 0.2% 0.3% 0.3% Whitening Agent0.004% 0.006% 0.002% 0.004% 0.02% water and miscellaneous balancebalance balance balance balance 100.0% 100.0% 100.0% 100.0% 100.0%

Exemplary Fabric Care Compositions

Table 3 provides examples of liquid fabric care compositions whichinclude at least one whitening agent of the present invention.

TABLE 3 Liquid Fabric Care Compositions Comprising the Present WhiteningAgent Ingredients 3a 3b 3c 3d Fabric Softening Active ^(a) 13.70% 13.70%13.70% 13.70% Ethanol 2.14% 2.14% 2.14% 2.14% Cationic Starch ^(b) 2.17%2.17% 2.17% 2.17% Perfume 1.45% 1.45% 1.45% 1.45% Phase Stabilizing0.21% 0.21% 0.21% 0.21% Polymer ^(c) Calcium Chloride 0.147% 0.147%0.147% 0.147% DTPA ^(d) 0.007% 0.007% 0.007% 0.007% Preservative ^(e)  5ppm  5 ppm  5 ppm  5 ppm Antifoam ^(f) 0.015% 0.015% 0.015% 0.015%Whitening Agent 30 ppm 30 ppm 30 ppm 15 ppm Tinopal CBS-X ^(g) 0.2 0.20.2 0.2 Ethoquad C/25 ^(h) 0.26 0.26 0.26 0.26 Ammonium Chloride 0.1%0.1% 0.1% 0.1% Hydrochloric Acid 0.012% 0.012% 0.012% 0.012% DeionizedWater Balance Balance Balance Balance ^(a)N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride. ^(b) Cationicstarch based on common maize starch or potato starch, containing 25% to95% amylose and a degree of substitution of from 0.02 to 0.09, andhaving a viscosity measured as Water Fluidity having a value from 50 to84. ^(c) Copolymer of ethylene oxide and terephthalate having theformula described in U.S. Pat. No. 5,574,179 at col. 15, lines 1-5,wherein each X is methyl, each n is 40, u is 4, each R¹ is essentially1,4-phenylene moieties, each R² is essentially ethylene, 1,2-propylenemoieties, or mixtures thereof. ^(d) Diethylenetriaminepentaacetic acid.^(e) KATHON ® CG available from Rohm and Haas Co. ^(f) Silicone antifoamagent available from Dow Corning Corp. under the trade name DC2310. ^(g)Disodium 4,4′-bis-(2-sulfostyryl) biphenyl, available from CibaSpecialty Chemicals. ^(h) Cocomethyl ethoxylated [15] ammonium chloride,available from Akzo Nobel.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A nonionic amphiphilic nitrogen-linkedpolyglycerol azo dye having the structure of Formula II:

wherein D is an aromatic or heteroaromatic group; wherein each R⁵ isindependently selected from the group consisting of oxyalkyl, oxyaryl,sulfonamidoalkyl, sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl,amidodiaryl, halogen, thioalkyl and thioaryl; wherein the index a isfrom 0 to 4; wherein each R is independently selected from the groupconsisting of H, (CH₂CH₂O)_(z′)H, and mixtures thereof; wherein groupsindicated by indices x, y and z may be arranged in any order; whereinx=0 to 10, wherein 1≤y≤5 and at least one y≥2; and wherein independentlyeach z=0 to 5 and each z′=0 to
 5. 2. A whitening agent according toclaim 1, wherein each R is independently selected from the groupconsisting of H, (CH₂CH₂O)_(z′)H, and mixtures thereof; wherein groupsindicated by indices x, y and z may be arranged in any order; whereinx=0 to 10, wherein 1≤y≤5 and at least one y≥2; and wherein independentlyeach z=0 and each z′=0.
 3. A whitening agent according to claim 1,wherein independently each x=0.